JPH0829617B2 - Transfer recording medium and image forming method - Google Patents

Description

The present invention relates to a novel transfer recording medium that can be used in copying machines, facsimiles, printers and the like, and an image forming method using the medium.

[Prior Art] In recent years, along with the rapid development of the information industry, various information processing systems have been developed, and recording methods and apparatuses suitable for the respective information processing systems have been developed. One of such recording methods is a heat-sensitive recording method. This method is widely used in recent years because the apparatus used is lightweight and compact, has no noise, and has excellent operability and maintainability.

Among these heat-sensitive recording methods, the heat-sensitive transfer recording method has recently attracted particular attention. This recording method generally uses a heat-sensitive transfer medium prepared by coating a sheet-like support with a heat-transferable ink in which a colorant is dispersed in a heat-meltable binder. A heat supply pattern is formed by superimposing the ink layer on the transfer medium so that the ink layer is in contact with the transfer medium, and supplying heat from the support side of the thermal transfer medium by a thermal head or the like to transfer the melted ink layer to the transfer medium. The transfer recording image according to the above is formed on the transfer medium. According to this method, plain paper can be used as the transfer medium.

[Problems to be Solved by the Invention] However, such a conventional thermal transfer recording method is not without drawbacks. In the conventional thermal transfer recording method, the transfer recording performance, that is, the image quality is greatly affected by the surface smoothness of the transfer medium, and good printing can be performed on the transfer medium having high smoothness, but the smoothness is low. This means that the print quality is remarkably deteriorated in the transferred medium. Moreover, even the most common transfer medium, paper with high smoothness is rather special, and ordinary paper has various degrees of unevenness due to the entanglement of fibers. Therefore, in the case of paper with large surface irregularities, the heat-melted ink cannot penetrate into the fibers of the paper at the time of printing and adheres only to the convex parts of the surface or its vicinity, resulting in sharp edges of the printed image. Or a part of the image is missing and the print quality is degraded.

Further, the transfer of the ink layer to the transfer medium is performed only by the heat from the thermal head, but generally the amount of heat that can be supplied from the thermal head is limited, and a large amount of recording signal is generated within a limited time. To convert and supply as a pulse, in order to prevent a time lag of cooling to a predetermined temperature within the heat pulse of the thermal head at the time of recording, and also to prevent a thermal stroke between the heat generating segments forming the thermal head surface. Theoretically, it was difficult to increase the amount of heat supplied from the thermal head. Therefore, high-speed recording has been difficult with the conventional thermal recording method.

In addition, since heat conduction has a slower response response than electricity or light, it is generally difficult to control the heat pulse until halftone can be reproduced when recording with a thermal head. Since the heat-sensitive transfer ink layer of No. 1 does not have transfer characteristics capable of expressing gradation, it was not possible to form a halftone recorded image.

The present invention can form a high-quality transfer image on a novel transfer recording medium that solves the above conventional problems, that is, the most commonly used plain paper having a low surface smoothness, and enables high-speed recording. An object of the present invention is to provide a transfer recording medium capable of halftone recording and multicolor recording.

[Means for Solving the Problems] The above object of the present invention has a distribution layer in which minute image forming elements having different color tones or optical densities are mixed on a substrate, and the image forming element is , A solid-state sensitive component that increases the melting temperature, softening temperature or glass transition point that governs the transfer characteristics of the image forming element when light energy is applied when the image forming element is heated. The transfer recording medium is characterized in that each of the image forming elements is covered with a wall material having spectral transmittance corresponding to the color tone or optical density of the element.

That is, in the formation of an image using the transfer recording medium of the present invention, the transfer image forming step and the transfer step are separated, and the transfer image is already formed in the transfer step. The restriction of No. is removed, and it is possible to apply the necessary and sufficient energy to the transfer recording medium in order to transfer a clear image according to the surface properties of the transfer medium. In addition, the transfer image formed in the previous step is
Since it is not a mere property change image such as a thermal fusion image, but an image formed by changing the physical properties that govern the transfer characteristics of the transfer layer, the transfer can be reliably performed by using this changed physical property difference. It can be realized and faithful transfer of the transferred image is also possible. For example, when a heat-melted image is used as a transfer image, it is necessary to completely maintain the heat-melted image from the transfer image forming step to the transfer step. However, a decrease in transferability due to a cooling phenomenon between both steps, Image blurring due to heat conduction to the periphery of the heat-melted image is inevitable. However, in the case of the present invention, the physical properties that govern the transfer characteristics, for example, the melting point, the softening point, the viscosity at the same temperature, etc. of the image forming element in the transfer recording layer are changed to form a transferred image. Is stored up to the transfer step, so that the transferability of the transferred image and image blurring do not occur unless energy for changing the physical properties is applied after the transfer image forming step. For this reason, even if the surface smoothness of the transfer medium is low, it is possible to form an image with high image quality, and the transfer image can be transferred to the transfer medium without degrading the image quality.

Further, in the formation of an image using the transfer recording medium of the present invention, application of signalized energy for transfer image formation and application of uniform energy for transfer are functionally separated. As compared with the case where the signalized energy for transfer image formation is used as the energy for transfer at the same time, the constraint condition of energy application is greatly relaxed. For example, the amount of energy for transfer image formation need only change the physical properties of the transfer recording layer, and
Since the energy for transfer may be uniform energy that is not signalized, it can be increased according to the desired transfer speed, and high-speed recording can be easily realized.

In the thermal head used in the conventional thermal transfer recording apparatus, even the fastest thermal response speed is about 1 to 5 msec, and if it is driven at a repetition cycle faster than that, the temperature rises and falls. The image quality could not be fully achieved within one cycle, and the effect of heat storage appeared on the image quality without insufficient heating or conversely the temperature did not drop. This was one of the most important factors that hampered speeding up, but if a plurality of types of energy are used as in the present invention, for example, if a thermal head and light irradiation are combined, then the transfer characteristics will be governed even in the state where heat is stored. Since the effectiveness of the heating state in changing the physical properties can be set only at the time of light irradiation, by applying light only during a limited time zone near the peak temperature, the temperature after the peak temperature can be reduced as in the past. It becomes possible to make the influence of the descending speed less likely to occur, and even if the conventional thermal head is used, the recording operation can be performed in a shorter repetition period, and high-speed recording becomes easier.

Further, since the image forming method according to the present invention forms a transfer image by applying a plurality of types of energy, the physical properties of forming the transfer image by that amount as compared with the conventional case where the transfer image is formed only by heat. The degree of change can be adjusted in stages, and the response response is quick as one of multiple types of energy, and the use of light that allows easy stepwise adjustment of intensity facilitates the formation of images that require halftone expression. become.

For example, by setting the intensity or time of light irradiation in three steps and combining it with heating, it is possible to express gradation in four steps (3 steps + non-heating).

Further, although it is desired that such control be performed at high speed, the fact that energy with a fast response response such as light can be used is also one factor that enables high-speed halftone recording.

In the formation of an image using the transfer recording medium of the present invention, the transfer image is formed by changing the physical properties that govern the transfer characteristics of the image forming element. This physical property depends on the type of transfer recording medium used. For example, in the case of a transfer recording medium in which a transferred image is transferred in a heat-melted state, it is a melting temperature, a softening temperature, a glass transition point, or the like. In the case of a transfer recording medium that is transferred to a transfer medium in a penetrating state, the viscosity is the same at the same temperature.

In addition, the plurality of types of energy used to form the transfer image are also arbitrarily determined depending on the type of the transfer recording medium used. For example, light, electron beam, heat, pressure, etc. are appropriately combined and used.

In the present invention, the transfer recording layer in which the physical properties governing the transfer characteristics are changed by the application of a plurality of types of energy means the pressure and heat or pressure and light used in Examples described later. A transfer recording layer in which the change of the physical properties is initiated by the application of a plurality of types of energy, and a description of the later-described FIGS. 2a to 2d and the transfer recording layer which causes the change in the physical properties by the application of light and heat. As shown in the constitutional example of 1., it includes both of the transfer recording layer in which the change of the physical properties is accelerated by plural kinds of energy.

Further, since the minute image-forming element coated with a wall material in a more uniform size forms the transfer recording layer, there is no variation in the color density of the formed image and the element is uniformly dispersed. And a clear image with little unevenness can be obtained.
In addition, when components that have the property of being softened or melted by being heated in the step of forming a transferred image, the wall material can prevent them from mixing with each other, so that a clear image with less bleeding can be obtained. It is possible to obtain.

Since the wall material has a predetermined spectral transmission characteristic, the image forming element covered with the wall material having a plurality of different spectral transmission characteristics mutually corresponds to different colors and optical densities, and multicolor recording or Even when halftone recording is performed, the wall material exerts a great effect in obtaining a clear image for the above-mentioned reason.

Furthermore, since the wall material has a wavelength-selective function, the wavelength-selecting function is not required for the image-forming components that are the equipment, so the degree of freedom in material selection is increased, and as a result, a high-sensitivity excellent image-forming component is obtained. It becomes easy to do. This is especially a clear multicolor image that improves the drawbacks such as the spectral characteristics of the color materials that make up the image constituents deteriorates the color tone due to the interaction with the spectral characteristics of the photosensitive material and the spectral sensitivity is difficult to achieve the desired characteristics. Can be obtained.

FIG. 1 shows a schematic structure of the transfer recording medium of the present invention.
The image forming element body 1aa having a component that changes the physical property that governs the transfer characteristics when energy is applied to the substrate 1 and a component of the colorant is bonded on the substrate 1 with the wall material 1al having a predetermined spectral transmittance. Attached with adhesive 1p.

Next, in order to explain the formation of an image using the transfer recording medium of the present invention, an example using a transfer recording medium in which a transfer image is formed by light and thermal energy is used, and FIGS. 2a to 2d are shown. The description will be made with reference. The time axes (horizontal axes) of the graphs in FIGS. 2a to 2d correspond to each other. Further, the image forming element contains, as a sensitive component, a polymerizing component containing a reaction initiator and a crosslinking agent described later. FIG. 2a shows how the surface temperature of the heating element rises and the temperature drops thereafter when the heating means such as a thermal head is developed and thermally driven for a time of O to t ₃ . The image-forming element on the transfer recording medium, which is in pressure contact with the heating element, shows a temperature change as shown in FIG. 2b with a temperature change of the heating element. I.e. t ₁
And the temperature with a time lag increases, similarly delayed from t ₃
It reached the highest temperature at the time of t _4, after the temperature is lowered. This transfer recording layer has a glass transition point Tg ₀ , and is abruptly softened and its viscosity is reduced in a temperature range of Tg ₀ or higher. This situation is shown by the curve A in FIG. 2c. After reaching Tg ₀ at time t ₂ , the viscosity continues to decrease until time t ₄ when the maximum temperature is reached, and the viscosity increases again with a decrease in temperature, and the viscosity sharply increases until time t ₆ when it decreases to Tg _0. . In this case, basically the physical properties of the image forming element did not change from those before heating, and the temperature Tg
_When heated to ₀ or higher, the same phenomenon of change in viscosity as described above is exhibited for the first time. Therefore, if the transfer recording layer is heated in contact with the medium to be transferred and heated for transfer, for example, Tg ₀ or higher, the transfer recording layer is transferred by a mechanism similar to the transfer mechanism of conventional thermal transfer recording. However, in the case of the present invention,
As shown in FIG. 2d, when the transfer recording layer is heated and irradiated with light from the time t _{2, the} reaction initiator contained in the transfer recording layer is activated by the irradiation of light, and the temperature changes the reaction rate. If the temperature rises high enough to increase the size, the reaction initiator acts to generate an activated cross-linking agent, which dramatically increases the probability of cross-linking the cross-linkable prepolymer, thus hardening the transfer recording layer. Advances.

When the heating and the light irradiation are simultaneously performed in this manner, the image forming element behaves as shown by the curve B in FIG. 2c. The crosslinking reaction glass transition point increases with advances, crosslinking is changed to Tg 'from time t ₅ the Tg ₀ ends. This is shown in Figure 2d. Therefore, if you heat in the next transfer process
A difference occurs in the physical properties (temperature dependence of viscosity) between the portion that has changed to Tg ′ and the portion that has not changed. Therefore, for example, Tg ₀ <Tr
When heated to a temperature Tr satisfying <Tg ′, a portion where the viscosity is lowered and a portion where the viscosity is not raised are generated, and only the portion where the viscosity is lowered is transferred onto the transfer medium. Although it depends on the temperature stability accuracy of the transfer step, Tg′-Tg _{0 at} this time is preferably about 20 ° C. or higher. In this way, the transfer image can be formed by controlling heating or non-heating according to the image signal and irradiating light at the same time. If the glass transition point changes, the softening temperature and the melting temperature also fluctuate with the same tendency. Therefore, the softening temperature and the melting temperature can be controlled by using the fluctuation range of the glass transition point as a guide.

With reference to the principle of the image forming method described above, the image forming method of the present invention will be described below with reference to FIGS. 3a to 3d.

The transfer recording medium 1 of the present invention is configured by providing a transfer recording layer 1a on a base film 1b. The transfer recording layer 1a
It is a layer in which minute image forming elements 1aa are mixed, and each image forming element 1aa exhibits a different color tone. For example, the first one showing the relationship between the transfer recording medium of the present invention and the thermal head.
In the embodiment as shown in FIGS. 3a to 3d, each image forming element 1aa
Contains a color material of any one of cyan (C), magenta (M), yellow (Y) and black (K). The coloring material contained in each image forming element 1aa is cyan,
The color material is not limited to magenta, yellow, and black, and any color material may be used depending on the application.
Each image forming element body 1aa contains, in addition to the coloring material, a sensitive component that changes physical properties that govern transfer characteristics when light and heat energies are applied.

The wall material of each image forming element body 1aa is configured to have different spectral transmittance depending on the contained coloring material. That is, the image forming element body 1aa containing the yellow coloring material,
When heat and light of wavelength λ _y are applied, crosslinking rapidly progresses and cures. Similarly, the image forming element body 1aa containing the magenta coloring material has heat and light of wavelength λ _m , and the image forming element body 1aa containing the cyan coloring material has heat and light of wavelength λ _c and black coloring material. The image forming element body 1aa containing a is crosslinked and hardened when heat and light of wavelength λ _k are applied respectively.

To form an image using the transfer recording medium of the present invention, the transfer recording medium 1 is superposed on the thermal head 20,
The light is radiated so as to cover the entire area of the heat generating part. The irradiation light has a wavelength with which the image forming element 1aa reacts, that is, a wavelength with which the wall material is selectively transmitted and the sensitive component reacts, and is sequentially irradiated. For example, when the image forming element 1aa is colored in any one of cyan, magenta, yellow and black, light having wavelengths λ _c , λ _m , λ _y and λ _k is sequentially irradiated.

That is, first, light having a wavelength λ _y is irradiated from the transfer recording layer 1a side of the multicolor transfer recording medium 1 and, for example, the heat generating resistors 20b, 20d, 20e and 20f of the thermal head 20 are caused to generate heat. Then, the image forming element body 1a containing the yellow coloring material
Of a, the image forming element body 1aa to which both heat and light of wavelength λ _y was applied (hatched portion in FIG. 3a; hereinafter, the cured image forming element body is indicated by hatching) is cured. To do.

Next, as shown in FIG. 3b, the transfer recording layer 1a is irradiated with light having a wavelength λ _m , and at the same time, the heating resistors 20a, 20e and 20f.
Of the image forming element body 1aa containing the magenta coloring material, the image forming element body 1aa to which heat and light of the wavelength λ _m are applied is cured. Further, as shown in FIGS. 3c and 3d, when light having a wavelength λ _c and light having a wavelength λ _k are respectively irradiated and a desired heating resistor is heated, an image formation where light and heat are applied is formed. The element body 1aa is cured, and a transfer image is finally formed on the transfer recording layer 1 by the image-forming element body 1aa which is not cured. This transferred image will be
As shown in the figure, it is transferred to the transfer medium 10.

In the transfer step, the transfer recording medium on which the transfer image is formed is brought into contact with the transfer target medium and heated from the transfer recording medium side or the transfer target medium side, and the transfer image is selectively transferred to the transfer target medium to form an image. To form. Therefore, the heating temperature at this time is selected so that only the transferred image is selectively transferred with respect to the physical properties that govern the transfer characteristics. It is also effective to apply pressure simultaneously in order to efficiently perform transfer. Pressurization, in particular,
This is effective when a transfer medium having a low surface smoothness is used. When the physical property that governs the transfer characteristic is the viscosity at room temperature, the transfer can be performed only by pressure as the energy applied in the transfer step. Heating in the transfer process
It is suitable for obtaining a stable multicolor image that is stable and has excellent storage stability.

As described above, in the embodiments described with reference to FIGS. 3a to 3d, the method of irradiating light to the entire area of the thermal head 20 and selectively heating the heating resistors of the thermal head 20 to form an image has been described. , Evenly heat a part of the transfer recording medium (
In the case of the thermal head 20 shown in FIG. 3a, a multicolor image can be similarly formed by selectively performing light irradiation when all the heating resistors are heated. That is, light energy of a wavelength that is modulated according to a recording signal and that is selected according to the color tone of the image forming element whose physical properties dominate transfer characteristics is desired is applied together with heat energy.

Explaining with the example shown in FIG. 3a, the heating resistors 20b, 20
Instead of heating d, 20e, and 20f, the thermal head 20 heats the whole uniformly, and the heating resistors 20b, 20d, 20f
The light having the wavelength λ _y is applied to the positions corresponding to e and 20f.
Also when irradiating with light of wavelength λ _m, the entire thermal head 20 is caused to generate heat and light is irradiated onto the positions corresponding to the heating resistors 20a, 20e and 20f. The same applies when irradiating with light of wavelength λ _c and wavelength λ _k .

In the above description, the thermal head is used as a means for uniformly heating the whole, but a uniform heating means such as a heat roll or a heating plate may be used.

Halftone recording using the transfer recording medium of the present invention
4D is a partial view showing the relationship between the transfer recording medium and the thermal head. The transfer recording medium 1 of the present invention shown in these figures has a transfer recording layer 1a on a base film 1b.
Is provided. The transfer recording layer 1a is a distribution layer of minute image-forming elements 1aa, and each image-forming element 1aa is colored with any one of a plurality of optical densities. In the example of FIGS. 4a to 4d, each image forming element
1aa is black and its optical density is D1 (0.12), D2 (0.2
7), D3 (0.80) and D4 (1.20). However, the optical density corresponding to each image forming element 1aa is not limited to D1, D2, D3, and D4, and any optical density may be used depending on the application. Further, in order to obtain a desired optical density, the amount of the coloring component contained in the image forming element may be changed, or the kind of the coloring component may be different. In addition to the colorant, each image-forming element 1aa contains a sensitizing component whose physical properties that govern the transfer characteristics change rapidly when light and heat energy are applied.

The wall material of each image forming element body 1aa is configured to have wavelength dependence according to different optical densities.

That is, the image-forming element body 1aa corresponding to the optical density of D1 is configured such that when heat and light of wavelength λ ₁ are applied, crosslinking rapidly progresses and cures. Similarly, the image forming element 1aa corresponding to the optical density of D2 has heat and light of wavelength λ ₂ , and the image forming element 1aa corresponding to the optical density of D3 has heat and wavelength λ _3.
Light, the image forming element body 1aa corresponding to the optical density of D4,
When heat and light of wavelength λ ₄ are applied, crosslinking proceeds and cures.

A halftone image is formed as described below using the transfer recording medium of the present invention.

That is, the transfer recording medium 1 is superposed on the thermal head 20, and light is irradiated so as to cover the entire heating portion of the thermal head 20. As the light to be applied, light having wavelengths λ ₁ , λ ₂ , λ ₃ and λ _{4 with which} the image forming element 1aa reacts is sequentially applied.

That is, first, while irradiating light of wavelength λ ₁ from the transfer recording layer 1a side of the transfer recording medium 1, for example, the thermal head 20
The heating resistors 20b, 20d, 20e, and 20f are heated. Then, of the image forming element 1aa according to the optical density of D1, the one to which both heat and light of wavelength λ ₁ are added (hatched portion in FIG. 4a: hereinafter, the cured image forming element The body is shown hatched). Next, as shown in FIG. 4b, when the transfer recording layer 1a is irradiated with light of wavelength λ ₂ and the heating resistors 20a, 20e, and 20f are heated, the image forming element body 1aa corresponding to the optical density of D2 is changed. Of these, those to which both heat and light of wavelength λ ₂ have been applied cure. Further, as shown in FIGS. 4c and 4d, while irradiating light with wavelengths λ ₃ and λ ₄ ,
When a desired heating resistor is heated, the image forming element body 1aa to which light and heat are applied is cured, and a transfer image is formed on the transfer recording layer 1 by the image forming element body 1aa that is not cured finally. . This transfer image is transferred to the transfer medium 10 in the next transfer step as shown in FIG. 2e. The transfer recording medium on which the transfer image is formed is brought into contact with the transfer target medium in the transfer step, and heating is performed from the transfer recording medium or the transfer target side, and the transfer image is selectively transferred to the transfer target medium 10 to form an image. To do. Therefore, the heating temperature at this time is determined so that only the transferred image is properly transferred with respect to the physical properties that govern the transfer characteristics. It is also effective to apply pressure simultaneously in order to effectively perform the transfer. Pressurization is particularly effective when a transfer medium having a low surface smoothness is used. When the physical property that governs the transfer characteristics is the viscosity at room temperature, the transfer can be performed only by applying pressure.

Further, in the above example, even if the optical densities of the four types of image forming elements having different spectral transmittances are equal, halftone recording can be performed by changing the quantity ratios and controlling the combination during transfer image formation. . It is easy to understand if this is explained using four types with the same quantity ratio. That is, by transferring all 4 types, 3 types, 2 types, and 1 type of elements from the high-density side, it is possible to realize halftone recording with one pixel in 5 steps (4 steps + non-transfer). If the quantity ratios are not equal, the number of combinations will increase and more multilevel expressions can be made.

Next, a transfer image obtained on the transfer medium as a result of the transfer process as described above will be described. As described above, in this embodiment, the transfer recording layer 1a is formed by distributing the image forming element bodies 1aa corresponding to the four kinds of optical densities D1, D2, D3 and D4. Table 1 shows the optical densities that can be obtained by combining these four types of image forming elements 1aa. According to Table 1, as shown in Fig. 2e, the thermal head 20
The optical densities of the transferred images transferred to the transfer medium 10 corresponding to the heating resistors 20a, 20b, ----- 20f are as shown in Table 2.

As described above, according to this method, it is possible to express a halftone by changing the optical density within one pixel.

In the above example, the case of having four types of optical densities has been described, but the number of types is not limited to four, and for example, the types of optical densities may be further increased. Further, the number of gradations can be further increased by combining some recording pixels in a matrix composed of a plurality of pixels with a conventional typical method for expressing halftone.

In the above description, as shown in FIGS. 3e and 4e, the respective image forming elements are discretely scattered on the transfer medium (recording paper etc.), but this is only for explanation. For convenience, the transferred element actually spreads two-dimensionally on the surface of the medium to be transferred, and as a result, corresponds to each heating element of the thermal head in the example of FIGS. 3a to 3d. To form each pixel correctly. Further, in the above-described example, the case where a plurality of energies are used in the transfer image forming step has been shown, but it is not always necessary that a plurality of energies are used, and light energy may be used for providing selectivity.

As the transfer recording medium used in the present invention, any transfer recording medium can be used as long as it can form a transfer image by a plurality of types of energy including light or a change in physical properties due to application of light energy. For example, a transfer recording medium containing a coloring component and a polymerizing component as a sensitive component in the image forming element may be used as a material whose physical properties such as the melting temperature, the softening point, the glass transition point and the viscosity are changed. By polymerizing the polymerizing component, the melting temperature and the like of the transfer recording layer at that portion becomes high, and the portion not polymerized forms a transfer image.

The polymerizing component is a component that causes a polymerization reaction or a crosslinking reaction, and typical examples thereof include the following monomers or polymers (a) to (c).

(A) Crosslinkable prepolymer, (b) Polymerizable prepolymer and crosslinker, (c) Polymerizable monomer or oligomer, Examples of the crosslinkable prepolymer include polyvinyl cinnamate, p-methoxycinnamic acid-succinic acid. Examples include half-esters, polyvinyl styrylpyridinium, polymethyl vinyl ketone, and the like.

Examples of the polymerizable prepolymer include epoxy resin,
Examples thereof include unsaturated polyester resin, polyurethane resin, polyvinyl alcohol resin, polyamide resin, polyacrylic acid resin, polymaleic acid resin, and silicone resin.

Examples of the cross-linking agent include ethylene glycol diacrylate, propylene glycol diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol diacrylate and N, N'-methylenebisacrylamide.

Examples of the polymerizable monomer include methyl acrylate, methyl methacrylate, cyclohexyl acrylate, benzyl acrylate, acrylamide, methacrylamide, N-methylol acrylamide, N-diacetone acrylamide, styrene, acrylonitrile, vinyl acetate, ethylene glycol diacrylate, and the like.
Examples thereof include butylene glycol dimethacrylate, 1,4-butanediol diacrylate, and 1,6-hexanediol dimethacrylate.

Examples of the polymerizable oligomer include diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol acrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, and the like.

When a polymerizable monomer or oligomer is used, a polymer such as cellulose acetate succinate or methyl methacrylate-hydroxyethyl methacrylate copolymer may be contained in order to improve the layer forming property.

In order to cause a reaction of the polymerized component, a reaction initiator is added as needed. As the reaction initiator, examples of the initiator acting by light energy include benzophenone, benzyl, benzoin ethyl ether, 4-N,
Carbonyl compounds such as N'-dimethylamino-4'-methoxy-benzophenone; organic sulfur compounds such as dibutyl sulfide, benzyl disfilled, decyl phenyl sulfide; peroxides such as di-tert-butyl peroxide, benzoyl peroxide; Carbon tetrachloride, silver bromide, 2-
Halogen compounds such as naphthalene sulfonyl chloride;
Nitrogen compounds such as azobisisobutyronitrile and benzenediazonium chloride; and the like.

Further, as a substance that receives thermal energy and acts as a reaction initiator, methyl hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, t-
Butyl cumyl peroxide, peroxyacetic acid, peroxybenzoic acid, acetyl peroxide, propionyl peroxide, isobutyryl peroxide, acetone peroxide, methyl ethyl ketone peroxide, diazoamine benzene, dimethyl-2,2'-azoisobutyrate, diphenyl sulfide, benzoyl Disulfide, etc. are mentioned.

In particular, the structure of the transfer recording layer in the case of forming a transfer image by receiving both light and thermal energy, the reaction rate of reaction rate by the reaction between the above-mentioned reaction initiator which acts upon receiving light energy and the polymerizing component. So that the combination has a large temperature dependence,
It suffices to select the type of reaction initiator and the polymerizing component.

For example, a combination of a polymerizable prepolymer having a functional group such as a copolymer of methacrylic acid ester or acrylic acid ester, a photosensitive cross-linking agent such as tetraethylene glycol diacrylate, and a reaction initiator such as benzophenone or Michler's ketone may be used. Can be mentioned.

The coloring component is a component contained to form an optically recognizable image, and various pigments and dyes are appropriately used. Examples of such pigments and dyes include inorganic pigments such as carbon black, yellow lead, molybdenum red and red iron oxide,
Hansa Yellow, Benzidine Yellow, Brilliant Carmine 6B, Lake Red C, Permanent Red F5R,
Examples thereof include organic pigments such as phthalocyanine blue, Victoria blue lake, and fast sky blue, and colorants such as leuco dyes and phthalocyanine dyes.

In addition, the transfer recording layer may contain a stabilizer such as hydroquinone, p-methoxyphenol, p-tert-butylicatechol 2,2-methylene-bis (4-ethyl-6-tert-butylphenol). .

Further, sensitizers such as p-nitroaniline, 1,2-benzanthraquinone, p-p'dimethylaminobenzophenone, anthraquinone, 2,6-dinitroaniline, and Michler's ketone are transferred to enhance activation of the reaction initiator against energy. It may be included in the recording layer.

As wall materials, cellulosics such as ethyl cellulose and nitrocellulose, nylon, tetron, polo urethane,
Polycarbonate, maleic anhydride type copolymer, vinylidene chloride, polyvinyl chloride, polyethylene, polystyrene, polymer type such as PET, gelatin, starch, wax and the like can be used. The above-mentioned polymerizing component, reaction initiator, coloring component, and other image forming components are coated with the materials used as the wall materials, which are the interfacial polymerization method and the in-situ method.
Method, in-liquid curing method, etc. (preferably the former two) chemical method, physical method such as coacervation method, phase separation method, submerged drying method, melt dispersion cooling method (preferably the former one) Air suspension method, spray drying method, electrostatic coalescence method, etc.
Person) mechanical method. Further, it is dyed with a coloring agent in order to have a desired spectral transmittance. As the colorant used here, the above-mentioned pigment or dye is appropriately used. Some examples of embodiments of the image forming method of the present invention will be given by taking such a transfer recording medium as an example. (1) Plural kinds of light sources having emission spectra corresponding to spectral transmittances of plural kinds of image forming elements Are applied to a transfer recording medium in correspondence with recording information to form transfer images having different melting temperatures.

(2) Using a plurality of light sources having emission spectra corresponding to the spectral transmissivity of a plurality of types of image-forming elements, at least one of light and thermal energy is applied in correspondence with recorded information, and the light and thermal energy are applied. Both are applied to form a transferred image having different melting temperatures and the like.

(3) A plurality of types of image forming components including a reaction initiator that acts upon receiving light and thermal energy and having different spectral transmittances, which are configured to mix a reaction initiator and a polymerizing component under pressure. For the image forming element coated with the wall material of
Under the condition that at least one of pressure, heat or light energy is applied in correspondence with the recorded information, the pressure, heat and light energy are applied to form a transferred image having different melting temperatures.

In the transfer step, the transfer recording medium on which the transfer image is formed in this manner is brought into contact with the transferred medium and heated from the transfer recording medium or the transferred medium side, and thus a portion having a low melting temperature, that is,
The transfer image formed in the non-polymerized portion is selectively transferred to the transfer medium to form an image. Therefore,
The heating temperature at this time is determined so that only the transferred image is selective for the physical properties that govern the transfer characteristics. It is also effective to apply pressure simultaneously in order to efficiently perform transfer. Pressurization is particularly effective when a transfer medium having a low plane smoothness is used. Further, when the physical property that governs the transfer characteristics is the viscosity at room temperature, transfer is possible only by applying pressure.

The above example shows the case where the melting temperature and the like of the portion to which a plurality of types of energy are applied becomes high, but as the transfer recording medium, a component that is softened by receiving a plurality of types of energy or has a low melting temperature and the like is used. If so, the portion receiving the energy forms a transfer image. Examples of such components include polymethyl vinyl ketone containing a ketone residue, a copolymer pair of methyl vinyl ketone or methyl isopropenyl ketone with ethylene, styrene, etc., polyvinyl phenyl ketone, polysulfone and the like.

Example 1 As shown in Table 3 of the image forming element y, benzozine yellow was used as a colorant and melt-mixed in a dark place to obtain an image forming component.

A mixture of this image-forming component with paraffin oil (the image-forming element / paraffin oil = (approximately) 20/1) 10 g of H
0.5 g of a surfactant having an LB value of 10 or more, 1 g of gelatin and gum arabic as the main components of the wall material and 0.4 g of phthalocyanine green as the colorant of the wall material are mixed in 200 ml of water and further mixed with a homomixer at 8,000 to 10,000 rpm. After stirring at
By adding ₄ OH (ammonia) and adjusting the PH to 11 or more, a microcapsule chiller is obtained, and the microcapsule chiller is separated by a Nutsche filter and dried at 35 ° C in a vacuum dryer for 10 hours, Particle size 7 to 15 μm (average 10
μm) powder (the image-forming element y (microcapsules) in which the image-forming components shown in Table 3 are coated with a wall material containing gelatin and gum arabic as the main components).

Further, the image forming components shown in Table 3 were melt mixed in the dark using Brilliant Carmine 6B as a colorant, and the image forming components were obtained by the same method as described above. Using this image-forming component, in the same manner as above except that dioxazine violet 23 was used as the colorant for the wall material, the particle size of 7-15
An image forming element M (microcapsule) having a size of 10 μm (average of 10 μm) was obtained.

Further, the image forming components shown in Table 3 were melt-mixed in the dark using phthalocyanine blue as a colorant, and the image forming components were obtained by the same method as described above. Using this image-forming component, a particle size of 7 to 15 μm (average of 10 μm) was obtained in the same manner as above except that a cobalt complex salt was used as a colorant for the wall material.
The image forming element C (microcapsule) of m) was obtained.

The above-mentioned three types of microcapsules are uniformly mixed, and are adhered in a layer form on a PET (polyethylene terephthalate) film having a thickness of 5 μm via an adhesive layer made of a polyester resin having a thickness of 5 μm. 6) was obtained.

Using the transfer recording medium thus obtained, a recorded image was created using an apparatus as shown in FIG.

The transfer recording apparatus shown in FIG. 5 is a line type of A4 size of 8 dots / mm, and 4 is a thermal head in which a heating element array is arranged at the edge part, and the transfer recording medium has a base material surface. It was installed so as to contact the thermal head 4. 3c, 3m and 3y are the spectral characteristics 3c ^* , 3m ^* and 3y shown in Fig. 7.
It is a light source with ^* and was installed several cm away from the position of the transfer recording medium during transfer recording. 3y is a fluorescent lamp for a diazo copying machine of 60 W using (SrMg) ₂ P ₂ O ₇ activated by Eu ^{++ as a} phosphor, and 3 m is (La, Ce, Tb activated by Tb ^{3 + as a} phosphor. )
_{It is} a 40W high color rendering green fluorescent lamp using ₂ O ₃ 0.2SiO ₂ 0.9P ₂ O ₅ , and 3c is a 60W Toshiba fluorescent lamp that emits black light. In order to obtain desired spectral characteristics, a sharp cut filter L-3818 was arranged in front of 3y and a sharp cut filter 1A19 was arranged in front of 3c. Transfer recording was performed using the transfer recording medium 1 (FIG. 6) by the transfer image forming step and the transfer step performed by the transfer recording apparatus described above. In the transfer image formation process, first, the heating element corresponding to the image signal yellow is not energized, and the portion corresponding to white of the image signal is energized at 0.8 W / dot for 2 mSec, and at the same time the diazo copying fluorescent lamp is used. Irradiation with 4 mSec was performed uniformly with 3y. After 1 mSec has passed from the end of this irradiation, the heating element corresponding to the magenta of the image signal is not energized, and 0.8 W is applied to the part corresponding to the white of the image signal.
High power color rendering green fluorescent lamp 3m at the same time as energizing 2mSec with / dot
Was uniformly irradiated for 4 mSec. After 1 mSec has passed after the end of this irradiation, the heating element corresponding to the cyan signal of the image signal is not energized, and the part corresponding to white of the image signal is energized for 2 mSec at 0.8 W / dot and at the same time the black light 3c is irradiated. Then, the transfer image formation for all three colors was completed. The above process was repeated at a cycle of 20 mSec / line.

In the transfer step, the recording paper 10 which is a plain paper having a surface smoothness of 10 to 30 seconds is superposed on the surface of the transfer recording medium 1 on which the transfer image is formed in the above step, on which the image forming element is attached. As shown in FIG. 5, an aluminum heat roll 8 whose surface is covered with 2 mm thick silicone rubber and whose surface temperature is kept at 90 to 100 ° C. by an internal heater 7 of 300 W, The transfer recording medium 1 was conveyed by those rollers and a stepping motor (not shown) while pinching with a pinch roll 9 which is a silicone rubber roll having a hardness of 50 ° and transferring the transfer image to the recording paper 10.

The image obtained on the recording paper 10 by the continuous execution of the above-mentioned transfer image forming step and the transfer step was a high-quality image with clear and good fixability.

Example 2 The image forming components shown in Table 4 in which the colorant is a black dye (DIARESIN BLACK B, manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) were melt mixed in a dark place, and the same method as in Example 1 was used. A powdery image-forming element was obtained. When the wavelength of light for initiating the reaction was examined by heating this image forming element to 80 ° C., it was in the range of about 380 to 500 μm. Further, when only this image forming element was transferred, the optical density of the image (optical density at this time is referred to as D10) was measured to be 0.60. Using this image-forming element, powder (microcapsules) having a particle size of 7 to 15 μm (average 10 μm) was obtained in the same manner as in Example 1 except that dioxazine violet 23 was used as the colorant for the wall material. It was

In addition, the image forming components shown in Table 5 in which the colorant is a dye (Dia resin black B manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) were melt-mixed in a dark place, and powdered by the same method as in Example 1. To obtain an image forming element. When the wavelength of light for initiating the reaction in this image forming element heated to 80 ° C. was examined, it was in the range of about 500 to 600 μm. Further, when only this image forming element was transferred, the optical density of the image (the optical density at this time is referred to as D11) was measured and it was 1.20. Using this image-forming element, powder (microcapsules) having a particle size of 7 to 15 μm (average 10 μm) was obtained in the same manner as in Example 1 except that Nitroso Green 8 was used as the coloring agent for the wall material. An equal mixture of the above two types of microcapsules was mixed with gelatin and gum arabic as a binder (equivalent mixture / binder = 90/10), and a polyimide film with a thickness of 6 μm (bar coater) was used. A transfer recording medium was obtained by applying a coating of 2 to 3 μm in a mosaic pattern.

Using this transfer recording medium, transfer recording was carried out by an apparatus in which two rows of shutter arrays 21 shown in FIG. 9 were installed at the positions shown in FIG. 8, and an image consisting of three-stage halftone was obtained.

In the transfer recording apparatus shown in FIG. 8, 17 is a heater for uniformly heating A4 size, 21 is a shutter array for selecting light, 22 is a 2 KW xenon lamp, and 1 is transfer recording. Light from a xenon lamp, which is a medium (not shown), was radiated through a shutter array only to a portion of the transfer recording medium in contact with the heater, and was blocked so as not to be radiated to other portions. The shutter array 21 is a two-row liquid crystal shutter array 21a, 21 as shown in FIG.
Each shutter 24 has an aperture size of 0.4 × 0.4 mm and an arrangement pitch of 0.5 mm. A yellow filter 25a is attached to the shutter array 21a, and a blue filter 25b is attached to the shutter array 21b.

Transfer recording using the transfer recording medium 1 was performed by the transfer image forming step and the transfer step performed by the transfer recording apparatus described above.

As a transfer image forming step, the above transfer recording apparatus is provided with
The transfer recording medium 1 is wound around the supply roll 2, and the polyimide film surface is placed so as to contact the heater 17, irradiation with the xenon lamp 22 is started, and the shutter of the shutter array 21a with the yellow filter 25a is attached. Of which optical density D
The one corresponding to the image signal of 10 is closed and the other shutter is 28 mS.
ec opened and then closed 12 mSec. At the same time, in one row of the shutter array 21b to which the blue filter 25b was attached, the shutter corresponding to the optical density D11 of the image signal one line before was closed and the other shutters were opened by 28 mSec and then closed by 12 mSec.
While repeating this 40 mSec / line step, in synchronization with the cycle of 40 mSec, the transfer recording medium 1 is covered with a stepping motor (not shown) and the surface thereof is covered with 2 mm thick silicon rubber, and the surface temperature thereof is 300 W. 90 by 7
Transported by the heat roll 8 kept at ~ 100 ° C,
Transfer images were continuously formed. As the transfer step, the recording paper 10 which is a plain paper having a surface smoothness of 10 to 30 seconds is superposed on the surface of the transfer recording medium on which the transfer image is formed by the above-mentioned step, on which the image forming element is adhered. As shown in FIG. 8, it is pinched by a heat roll 8 and a pinch roll 9 which is a silicone rubber roll having a hardness of 50 °, and while transferring the transferred image to the recording paper 10, those rollers and stepping (not shown) are carried out. The transfer recording medium 1 was conveyed by a motor.

The image thus obtained on the plain paper was a clear image in which the density (brightness) of the black dye was clearly divided into three stages, and was a high-quality image with good fixability.

[Advantages of the Invention] As described above, in the present invention, since a transfer image is formed using light energy, a high-speed and high-definition image can be obtained.

In addition, it is possible to use a transfer recording medium whose properties change only when a combination of light and other energies, that is, when a plurality of types of energy are applied at the same time. As compared with the method that uses only heat to obtain, the environmental stability is higher and it is possible to always stably obtain a high-definition image. For this reason, the preservability of the transfer recording medium and the preservability of the recorded image are improved.

Since the process of forming the transfer image and the process of transferring the transfer image are independent, the conditions suitable for transferring the transfer image to the transfer medium with high quality and stability can be freely set independently of the conditions for forming the transfer image. It is possible. Therefore, it is possible to obtain a high-quality image not only on the medium to be transferred but also on a wide range of transfer media such as paper having low surface smoothness and transparency.

Further, in the transfer recording medium of the present invention, since each image forming element is separated by the wall material and is discontinuous, it is possible to obtain a sharp image and obtain a clear image, and to form a multicolor image. Also in, it is possible to obtain a high-quality image with vivid colors.

Further, since the image forming element is covered with the wall material having a predetermined spectral transmittance, it is easy to set the spectral characteristics sharply, and as a result, the transferred image can be formed with high accuracy. High-quality multicolor and halftone images can be obtained. Further, since the image forming component is not required to have a spectral characteristic, a pure color can be obtained and a clear image with high saturation can be obtained.

[Brief description of drawings]

FIG. 1 is a sectional view of the transfer recording medium of the present invention, and FIGS. 2a to 2d are graphs showing changes in physical properties of the transfer layer of the transfer recording medium of the present invention due to application of light and heat. FIGS. 3 to 3e show a transfer process of the transfer recording medium of the present invention containing cyan, yellow, magenta and black as coloring materials, and FIGS. 4a to 4e show colors of similar colors. FIG. 5 shows a transfer process of the transfer recording medium of the present invention containing a material, and FIG. 5 shows an apparatus for transferring the transfer recording medium of the present invention containing cyan, yellow and magenta as color materials. FIG. 6 is a plan view and a sectional view of a transfer recording medium of the present invention containing cyan, yellow, magenta and black as coloring materials, and FIG.
9 is a graph showing the spectral characteristics of three light sources of the transfer recording apparatus shown in FIG. 8, FIG. 8 is an apparatus for transferring the transfer recording medium of the present invention containing a coloring material of a similar color, and FIG. [Fig. 4] is a plan view of a shutter array. 1: Transfer recording medium 1a: Transfer recording layer 1al: Wall material 1aa: Image forming element body 1b: Substrate 1p: Binder material 2: Supply roll 3c: Black light (Toshiba fluorescent lamp) 3y: Diazo copy machine fluorescent lamp 3m: High color rendering green fluorescent lamp 3c ^* : Spectral characteristics of black light 3y ^* : Spectral characteristics of fluorescent lamp for diazo copying machine 3m ^* : Spectral characteristics of high color rendering green fluorescent lamp 4: Thermal head 5: Control circuit 6: Image signal 7: Internal heater 8: Heat roll 9: Pinch roll 10: Transfer medium 11: Take-up roll 12: Image 13: Lighting control circuit 14: Lighting control signal 15: Sharp cut filter 1A19 16: Sharp cut filter L- 3818 17: Heater 18: Shield control device 19: Image signal 20: Thermal head 20a, 20b, 20c, 20d, 20e, 20f: Heating resistor 21, 21a, 21b: Shutter array 22: Xenon lamp 23: Transfer recording medium 24: Shutter 25a: Yellow filter 25b: Blue filter A: Change in viscosity without light irradiation B: change in viscosity of the irradiated with light C: heating time D: light exposure time E: 1 cycle time _{λ c, λ m, λ y} , λ k, λ 1, λ 2, λ 3, λ 4: Each Wavelengths that the image-forming elements of

Claims (4)

[Claims] 1. A distribution layer having a mixture of minute image-forming elements exhibiting different color tones or optical densities on a substrate,
The image forming element is a solid whose melting temperature, softening temperature or glass transition point that governs transfer characteristics of the image forming element is increased by applying light energy when the image forming element is heated. A transfer recording medium, which has a sensitizing component, and each of the image forming elements is covered with a wall material having a spectral transmittance corresponding to a color tone or an optical density exhibited by the element. 2. The transfer recording medium according to claim 1, wherein the different color tones are cyan, magenta and yellow. 3. The transfer recording medium according to claim 1, further comprising a composition in which a reaction initiator and a polymerizing component are mixed as a sensitive component under pressure. 4. A distribution layer formed by mixing fine image-forming elements exhibiting different color tones or optical densities on a substrate,
The image forming element is a solid whose melting temperature, softening temperature or glass transition point that governs transfer characteristics of the image forming element is increased by application of light energy when the image forming element is heated. Light energy is distributed to a transfer recording medium that has a sensitizing component in the form of a line and each of the image forming elements is covered with a wall material having spectral transmittance corresponding to the color tone or optical density of the element. Under the condition that the layer is heated, at least one of light energy and heat energy is applied to the recorded information so that both energy is applied, and by heating the distribution layer, both light energy and heat energy are generated. An image forming method comprising a step of transferring a distribution layer of a portion other than the applied portion onto a transfer medium.